Novel method for treating industrial processing water



United States Patent 3,364,141 NQVEL METHGD FOR TREATING INDUSTRIAL PROCESSING WATER Herman Berenson, Trenton, N.J., Albert Carl Dornbush,

Pearl River, N.Y., and Donald Clifford Wehner, Fairfieid, Qonrn, assignors to American Cyanarnid Company, Stamford, Conn, a corporation of Maine No Drawing. Original application Aug. 23, 1965, Ser. No. 481,941. Divided and this application July 27, 1967, Ser. No. 656,334

3 Claims. (Cl. 21064) ABSTRACT 6F THE DISCLOSURE The invention is directed to a method for treating industrial processing water to control the growth of microbial, algae or fungi organisms therein comprising: adding to said processing water a growth inhibiting amount of a compound of the formula:

wherein X represents an anion and where n is an integer of from 6 to 14.

The instant application is a divisional of copending application, Ser. No. 481,941, filed on Aug. 23, 1965.

The instant invention relates to novel antimicrobial, fungicidal and algicidal compositions and to methods for their use. More particularly, it relates to such biocidal compositions containing as the active component thereof an a,w-al'kylenebis[triphenylphosphonium salt] and to methods for controlling the growth of such diverse organisms as bacteria, fungi and algae.

Many antimicrobial, fungicidal and algicidal compositions are presently known. However, few such compositions exhibit broad spectrum activity for demanding use under an ever widening variety of conditions. For instance, many algicides for use in treatment of tower cooling Waters as well as pool waters are not effective over a protracted time period clue to the presence of oxidants, such as chlorine, which cause their ready degradation. In swimming pools and in industrial Waters used in cooling towers for air conditioning, algae are a considerable problem. They produce mats of slime which restrict the flow of water through heat exchangers, serve as food for bacteria, cause slippery, hazardous conditions in pools and are unsightly. Chlorine is normally added to swimming pools in amounts ranging from about 0.1 to about 0.5 part per million and often to cooling waters for bacterial control but many algae species are chlorine resistant to the low levels of chlorine used. Higher levels of chlorine are not useable because of eye and mucous membrane irritation in pools and corrosion inducing prop- I erties in cooling water systems. Where higher levels of chlorine are used, known algicides are generally degraded and destroyed.

Biocidal compositions to be useful should be etfective against an encountered organism which is to be controlled. In this connection, the compositions should be (a) safe to handle and (b) stable under those conditions prevailing at the point of contact or application. It is, therefore, a principal object of the invention to provide such compositions and to provide methods for their use.

In accordance with the present invention, it has been surprisingly found that compositions containing as an active ingredient thereof the compound of the general formula:

wherein n is an integer from 6 to 14 and X represents an anion, such as, for instance, perchlorate, nitrate, sulfate, chloride, bromide, iodide, R0803, ROSO, or RS0 Where each R is alkyl or aryl, are highly effective under a wide variety of conditions. Unexpectedly, the high level of activity of compositions of the present invention against a large variety of pathogenic organisms coupled with good water solubility, low phytotoxicity, good stability to heat, light, chemical oxidants, fabric softeners and detergents cogently points up the markedly enhanced disinfectant and sanitizing properties of the aforementioned compositions.

In general, the active algicidal, fungicidal and antimicrobial compounds employed in the process of the invention are prepared in a straightforward manner by heating an alcoholic solution containing one mole of an ap propriate u,w-dihaloalkane with about two or more moles of triphenyl phosphine. Resultant product is then recovered as by filtration or by precipitation with ethyl ether.

In the preparation of the identified compositions, either a suitable alkane dialkyl sulfonate ester or an alkane diarylsulfonate ester can be substituted for the u w dihaloalkane reactant to .yield the corresponding alkyl sulfonate or aryl sulfonate salts, respectively, of the identified compositions. Other salts, such as acetates, nitrates, sulfates or perchlorates, can be prepared from the resultant dihalide, for example, by well-known exchange reactions.

r salts] contemplated by the invention are:

chlo- Advantageously, a wide range of growth inhibiting amounts of salt herein contemplated may be admixed with an inert carrier applied to an area to be treated. Thus, in treating swimming pool water, a small, but effective, amount from 1 to parts per million (p.p.m.) of the salt can be added to the water to be treated either as such or diluted with a major amount of water to inhibit algae growth. Minor amounts of salts may also be incorporated into major amounts of other diverse extenders, such as starch, natural gums, agar, commercially available synthetic detergents of the anionic or non-ionic types.

wherein the lowest concentration, in parts per million, of test compound found to produce 100% control of the test organism is presented.

TABLE I C ompound P.p.m. Organism Candida albicans. Saccharomyces cereviszae. Muco'r ramanm'a'aus. Hormodmdrum cladasporotdes. Tn'chophyton mentagroplwtes. lllz'crospomm gy pseum. Penicilliam digztatum. Memnoniella echi'aata. Chaetomiam globosam. Aspergillas fumigatas.

For use in the latter detergent extender, as much as 300 p.p.m., or more, can be tolerated to inhibit microbial growth.

The invention will be further illustrated in conjunction with the following examples which are to be taken as illustrative only and not by way of limitation. All'parts are by weight unless otherwise noted. 7

A typical preparation ofthe illustrative biocidal compounds is presented below.

EXAMPLE 1 Preparatiori of 1,10-decamethylenebis[triphenylphosphonium bromide] A mixture of 110 parts of triphenyl phosphine, 60 parts of 1,10-dibromodecane, and 100 parts (by volume) of n-butyl alcohol are refluxed in a suitable reaction vessel for 18 hours, then cooled to permit the addition of diethyl ether. From this mixture a tacky product precipitated, is separated from the ether and dissolved in a minimum amount of n-butyl alcohol and again reprecipitated from diethyl ether. The precipitate is dissolved in 250 cc. of boiling n-butyl alcohol, then cooled and treated with diethyl ether. The purified product had a melting point of 232 C. to 234 C.

EXAMPLE 2 Antifungal activity of the compounds of the instant invention is demonstrated in the following tests wherein accurately weighed amounts of 1,10-decamethylenebis [triphenyl-phosphonium bromide] are placed in test tubes and dissolved or suspended in predetermined quantities of sterile, hot 'fluid asparagine agar (meat ex- Substituting for the test compound in Table I, 1,8-

octamethylenebis[triphenylphosphonium bromide], substantially the same results as reported in Table I are noted.

" EXAMPLE 3 reported as the lowest concentration of test compound a which produces 100% bacterial control.

Activity of the compounds of the invention against anaerobic bacterial is determined 'by a broth dilutioni 7 method of assay. In this method, graded levels of 1,10 decamethylenebis [triphenylphosphonium bromide] in one milliliter of solution are added to 9 milliliters of thioglycollate medium. The solutions are inoculated with the organism Clostridz'um sporogenes and incubated for 48 hours at 37 C. At the end of the incubation period, the solutions are examined. Those found to be clear with no growth areread as active, those which are cloudy or have a characteristic odor are read as inactive. As in.

Example 1, results are reported as the lowest concentration of compound found to produce 100% control of the test organism in Table 11 below.

TABLE II Compound P.p.m. Organism Mycobacterium smegmatzs. Staphylococcus aura-21s.. Streptococcus faecalis Bacillus subtilis }Gram-Positive.

Proteus vulgaris Salmonella gallinarmn.

C'Zostridium sporogenes Anaerobic.

tract, 2.0 grams; asparagine, 0.5 grams; dibasic potassium phosphate, 0.5 gram; agar, 20.0 grams; water, q.s.

to 1000'milliliters with no pH adjustment) to provide known concentration test material in the agar;

The contents of each tube are thorougly mixed and poured into etri dishes to harden. Aqueous suspensions of the test cultures of fungi are then streaked upon the surface of the agar and permitted to incubate for 48 or 96 hours. After incubation, all plates are examined and the results recorded. Controls are prepared in the same manner as stated above with the exception that the agar employed is free of test compound. Cultures of each test organism are also streaked on the control agar surface and are found to proliferate profusely.

.. EXAMPLE 4 Laundry washing tests are carried out in screw-capped, 8-ounce wide-mouth jars with agitation provided by a reciprocating machine operating at 180 cycles per minute.

To each jar is added 20 milliliters of hot (60 C.), 0.25 f w./v. aqueous non-germicidal, anionic synthetic deter-r gent, that is a built, alkyl aryl sodium sulfonate all purpose, granular detergent solution, and .3 or 4 glass beads. The jars and contents are then sterilizedforlS minutes at 121 C., cooled, placed in a water bath at 60 C. and 1 milliliter of an acetone solution containing 0.1 milligram 1,IO-decamethylenebis[triphenylphosphonium bromide] is added. (The germicide concentration is Results of the tests are recorded in Table I below thus 5 p.p.m. with respect to thewash water, or expressed Escherichia 00111;. }Gram-Ncgativo.

in terms of the weight of detergent, the concentration is 0.2%.). Twenty 1-inch diameter circular discs of unbleached cotton fabric, weighing about 1.0 gram, are added, the jars briefly swirled to distribute the circles, and transferred to the reciprocating shaker. Jars are shaken for minutes at the end of which time the wash water is next decanted and replaced with 100 milliliters sterile water at room temperature. The simulated rinse cycle lasts one minute. The rinse water is decanted and the circles transferred to sterile wire screens and dried for 30 minutes at 50 C. to 55 C.

Cotton fabrics so laundered are imparted with an antibacterial finish as evidenced by their failure to support growth when inoculated with a suspension of a viable culture of Staphylococcus aureus or Brevibacterium ammoniagenes implanted on the surface of a solidified nutrient agar and incubated 48 hours at 37 C.

Similar results are obtained utilizing 1,12-dodecamethylenebis[triphenylphosphonium chloride] in lieu of 1,10-decamethylenebis[triphenylphosphonium bromide].

Control fabrics similarly laundered but in the absence of a germacide supported luxuriant growth of Staphylococcus aureus and Brevibacterium ammoniagenes.

EXAMPLE 5 Cotton cloth circles are laundered as described in Example 4 above. The cloth to liquor ratio is maintained at 1:20, respectively, and germicide concentration at 5 p.p.m. with respect to wash water. However, 0.1 milliliter of bleach solution, diluted 20 percent with water, is added after the germicide addition, but prior to adding the cotton circles. The laundry bath now contains about 200 p.p.m. of available chlorine. Cotton circles are then added, subjected to the wash, rinse, and drying steps as previously described, and inoculated with a suspension of viable Staphylococcus aureus. Cotton fabric so treated and incubated 2 days at 37 C. on nutrient agar failed to support bacterial growth. In contradistinction, luxurious growth of Staphylococcus aureus is obtained when control swatches washed in the detergent alone or in detergent containing 5 p.p.m. of 3,4,4-trichlorocarbanilide are similarly incubated on nutrient agar.

EXAMPLE 6 Cotton swatches are washed as described in Example 5 in the ger-micide-detergent system with about 200 p.p.m. available chlorine present. Samples are dried at 50 C. to 55 C. for 30 minutes and then autoclaved for minutes at 121 C. Cotton swatches so treated effectively suppressed the growth of Staphylococcus aureus, whereas control fabric Washed in the absence of germicide supported growth of Staphylococcus aureus at a density of 3000 to 4000 colonies per square inch.

EXAMPLE 7 Cotton circles washed and dried as described in Example 5 are subjected to ultra-violet irradiation for 2 hours at a distance of one meter from the lamp. (This exposure is equivalent to 8 hours of sunlight.) Samples so treated failed to support growth of Staphylococcus aurcus, whereas control fabrics laundered in non-germicidal detergent and similarly exposed to ultra-violet irradiation supported luxurious growth.

EXAMPLE 8 Cotton swatches are laundered as described in Example 5 except that the final germicide concentration is now 1.67 p.p.m. with respect to the wash water (0.067% on the detergent weight) instead of 5 p.p.m. The rinsed and dried samples are inoculated with a suspension of a viable culture of Bnevibacterium ammoniagenes, implanted on nutrient agar, and incubated for 2 days at 30 C. No bacterial growth is evident on samples so treated, whereas control swatches laundered in non-germicidal detergent with 200 p.p.m. available chlorine supported the growth of more than 2000 colonies per square inch.

6 EXAMPLE 9 Antibacterial activity TABLE III Minimum Inhibitory Concentration (in meg/ml.) of 1,10-deca- Test Micro-orga-uism methylenebis[triphenylphosph onium bromide] Bordetella brmchiseptica 25 Escherichia roli 25 Salmonella gallinarzm 125 Salmonella typhosa.-- 5 Staphylococcus aureus i- 1 EXAMPLE l0 Antifungal activity against plant pathogens The activity of the compounds of the instant invention against the organisms Monilinz'a fructicola, the pathogen that incites American brown rot of stone fruit, Stemphylium sarcinaeforae, the pathogen responsible for leafspot of several legumes and Aspergillus niger, a saprophyte which degrades textiles, fabrics, leather and stored fruits and vegetables, is demonstrated by the following test wherein sufficient amounts of 1,10=decamethylenebis [triphenyl-phosphonium bromide] are dissolved or suspended in water to provide dilutions of p.p.m., l0 p.p.m. and 1 p.p.m. of test compound in solution when 0.4 ml. of solution is added to 3.6 ml. of a spore suspension of the test organism.

Separate spore suspensions of the above-identified pathogens are prepared from 7 to 10-day cultures of the organisms grown on potato-dextrose agar slants. The spores are washed from the agar slants with distilled water and are adjusted to a concentration of approximately 50,000 spores per cc. of water. Two ml. of orange juice is added per liter of spore suspension to facilitate germination. To opticlear vials, 0.4 ml. of solution of test compound is added along with 3.6 ml. of spore suspension. The vials are then placed on a tumbler and the tumbler rotated to assure contact of chemical and organism. At the end of a 24-hour exposure period, the suspensions are examined microscopically to determine if germination has occurred. The results of the above test are recorded in Table IV below.

TABLE V Amount of toxicant Algae: in ppm.

Black algae (a chlorine resistant bluegreen) 1.5

Ankistrodesmus species (green) 0.8

Clamydomonas species (green) 0.8

Similar results are obtained employing 1,16-hexadecamethylenebis [triphenylphosphonium chloride] in lieu of the toxicant used in this example.

EXAMPLE 12 Cotton fabrics are laundered following the procedure of Example 4, except that they are subjected to a total of three rinses and dried. It is noted that the so-laundered fabrics fail to support growth of S. aureus, whereas the control fabrics similarly laundered without any germicidal additive support luxurious growth. A durable antibacterial finish is thus imparted to the laundered fabrics by the exemplified biocidal compounds. So-treated fabrics are particularly well suited for use under conditions requiring a substantial degree of bacterial control.

It is believed that the durability of the fabrics finish is due to the substantivity of the compositions defined above.

EXAMPLE 13 This example demonstrates the effect of 1,10-decamethylenebis[triphenylphosphonium bromide] in con- 8' trolling the organism, Pityrosporum ovale, which is readily isolated from the human scalp.

Activity against Pityrosporum ovale is determined by an agar dilution method in which graded levels of 1, 10-

decamethylenebis[triphenylphosphonium bromide] are dissolved in molten Emmons agar (1% neopeptone, 4% dextrose and 2% agar) and poured into Petri dishes to harden. A suspension of P. ovale in sterile corn oil is streaked over the surfaceof the hardened plates and incubated for 72 hours at 30 C. At the end of this time, plates are examined. It is noted that as little as 100 parts per million of the compound suppress the growth of the aforementioned organism.

We claim:

1. A method of treating industrial processing water to control the growth of microbial, algae or fungi organisms therein comprising: adding to said processing water a growth inhibiting amount of a compound of the formula:

References Cited FOREIGN PATENTS 12/1964 Germany.

OTHER REFERENCES Chem. Abstracts 61: 142670 (1964).

MICHAEL E. ROGERS, Primary Examiner. 

